Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education of the People's Republic of China, Heilongjiang University, Harbin, 150080, P.R. China.
Angew Chem Int Ed Engl. 2016 Jan 26;55(5):1830-4. doi: 10.1002/anie.201508505. Epub 2015 Dec 21.
Phosphorus-doped hexagonal tubular carbon nitride (P-TCN) with the layered stacking structure was obtained from a hexagonal rod-like single crystal supramolecular precursor (monoclinic, C2/m). The production process of P-TCN involves two steps: 1) the precursor was prepared by self-assembly of melamine with cyanuric acid from in situ hydrolysis of melamine under phosphorous acid-assisted hydrothermal conditions; 2) the pyrolysis was initiated at the center of precursor under heating, thus giving the hexagonal P-TCN. The tubular structure favors the enhancement of light scattering and active sites. Meanwhile, the introduction of phosphorus leads to a narrow band gap and increased electric conductivity. Thus, the P-TCN exhibited a high hydrogen evolution rate of 67 μmol h(-1) (0.1 g catalyst, λ >420 nm) in the presence of sacrificial agents, and an apparent quantum efficiency of 5.68 % at 420 nm, which is better than most of bulk g-C3 N4 reported.
磷掺杂六方管状碳氮化物(P-TCN)具有层状堆积结构,由六方棒状单晶超分子前体(单斜晶系,C2/m)获得。P-TCN 的制备过程包括两步:1)在磷钼酸辅助的水热条件下,由三聚氰胺原位水解,三聚氰胺与三聚氰胺氰尿酸自组装制备前驱体;2)在加热下从前驱体中心引发热解,从而得到六方 P-TCN。管状结构有利于增强光散射和活性位。同时,磷的引入导致带隙变窄和电导率增加。因此,在牺牲剂存在的情况下,P-TCN 表现出 67 μmol h-1(0.1 g 催化剂,λ >420nm)的高析氢速率,在 420nm 处的表观量子效率为 5.68%,优于大多数报道的块状 g-C3N4。